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INTRODUCTION

The threat of global warming has fuelled worldwide efforts to develop technology that reduces
carbon dioxide emissions. CO2 conversion and utilization are an important element in chemical
research on sustainable development because CO2 also represents an important source of
carbon for fuels and chemical feedstock in the future. The prevailing thinking for CO2
conversion and utilization begins with the use of pure CO2, which can be obtained by
separation. In general, CO2 can be separated, recovered and purified from concentrated CO2
sources by two or more steps based on either absorption or adsorption or membrane separation.
Even the recovery of CO2 from concentrated sources requires substantial energy input.
According to US DOE, current CO2 separation processes alone require significant amount of
energy which reduces a power plant’s net electricity output by as much as 20%.

This report discusses a new process concept that has been recently proposed for effective
conversion of CO2 in the flue gases from electric power plants without CO2 pre-separation,
which can be used for the production of synthesis gas (CO + H2) with desired H2/CO ratios
for synthesizing clean fuels and chemicals. The tri-reforming concept represents a new way of
thinking both for conversion and utilization of CO2 in flue gas without CO2 separation, and
for production of industrially useful synthesis gas with desired H2/CO ratios using flue gas and
natural gas.

The idea of separating and capturing CO2 from the flue gas of power plants did not start with
concern about the greenhouse effect. Rather, it gained attention as a possible economic source
of CO2, especially for use in enhanced oil recovery (EOR) operations where CO2 is injected
into oil reservoirs to increase the mobility of the oil and, therefore, the productivity of the
reservoir. Several commercial CO2 capture plants were constructed in the late 1970s and early
1980s. When the price of oil dropped in the mid-1980s, the recovered CO2 was too expensive
for EOR operations, forcing the closure of these capture facilities. To date, all commercial CO2
capture plants use processes based on chemical absorption with a monoethanolamine (MEA)
solvent. MEA was developed over 60 years ago as a general, non-selective solvent to remove
acid gases, such as CO2 and H2S, from natural gas streams. The process was modified to
incorporate inhibitors to resist solvent degradation and equipment corrosion when applied to
CO2 capture from flue gas. Also, the solvent strength was kept relatively low, resulting in large
equipment sizes and high regeneration energy requirements.
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2. SOURCES OF CO2 EMISSIONS

The combustion of fossil fuels is the primary source of CO2 emissions. The three major fossil
fuels used worldwide are coal, petroleum, and natural gas. According to government reports,
from 1980 to 1997, the end-use total from different sectors (e.g., residential, commercial,
industrial, and transportation) have shown a steady increase in CO2 emissions. The top 10
major producers of CO2 in terms of total annual emissions (in alphabetical order) are Canada,
China, Germany, India, Italy, Japan, Russia, South Korea, the United Kingdom, and the
United States.

Carbon dioxide is produced by combustion of coal or hydrocarbons, the fermentation of


sugars in beer and wine making, respiration of all living organisms. Emission from
volcanoes, hot springs, geysers and other places where the earth's crust is thin and is freed
from carbonate rocks by dissolution.

Carbon dioxide emissions are one of the main factors responsible for global warming. It
results in melting of glaciers, increasing sea water level, and climate change. The upper
safety limit for atmospheric CO2 is 350 ppm. But atmospheric CO2 levels have stayed higher
than 350 ppm since early 1988. Today, the rate of increase of atmospheric CO2 is more than
100 times faster than the increase that occurred when the last ice age ended. For the past ten
years, the average annual rate of increase is 2.07 ppm.

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3. CO2 CAPTURE/SEPARATION SYSTEMS

3.1 POST COMBUSTION CAPTURE

Post-combustion Capture refers to capturing carbon dioxide from flue gas after the fossil fuel
(e.g., coal, natural gas, or oil) has been burned. Of the 4 trillion kilowatt hours of electricity
generated in the U.S. in 2015, about 33% was from coal. In conventional coal-fired power
plants, coal is burned with air in a boiler producing steam to rotate a turbine generator and
produce electricity.

The biggest challenge in post-combustion capture is separating CO2 generated during


combustion from the large amounts of nitrogen (from air) found in the flue gas. In this area,
the R&D effort is focused on advanced solvents, solid sorbents, and membrane systems. In
addition, novel concepts, for instance hybrid technologies that efficiently combine attributes
from multiple key technologies (e.g., solvents and membranes) are being investigated.

Solvent-based CO2 capture involves chemical or physical absorption of CO2 from flue gas into
a liquid carrier. The absorption liquid is regenerated by increasing its temperature or reducing
its pressure to break the absorbent-CO2 bond. High levels of CO2 capture are possible with
commercially-available chemical solvent-based systems; however, these systems require
significant amounts of energy for regeneration. R&D objectives include advanced solvents that
have a lower regeneration energy requirement than existing amine systems, and that are also
resistant to the flue gas impurities.

Sorbents are being explored for post-combustion CO2 capture and potentially offer advantages
over conventional aqueous solvent-based processes (e.g., such as lower regeneration energy
requirements due to the heat capacity for solids being significantly lower than that of water).
R&D objectives include low-cost durable sorbents that have high selectivity for CO2, high
CO2 adsorption capacity, and can withstand multiple regeneration cycles.

Cryogenic separation is a physical process that separates CO2 under extremely low
temperature. It enables direct production of liquid CO2 at a low pressure, so that the liquid
CO2 can be stored or sequestered via liquid pumping instead of compression of gaseous CO2

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to a very high pressure, thereby saving on compression energy. During the cryogenic separation
process, the components of gas mixtures are separated by a series of compression, refrigeration,
and separation steps. Since all these steps are highly mature technologies in the chemical
industry, their operation and design feasibility can be guaranteed. The cryogenic separation
process requires no chemical agent, hence avoiding secondary pollution. As far as industrial
application is concerned, gas mixtures are usually composed of CO2 and other gases, the
boiling points of which are relatively low. These gases include H2, N2, O2, Ar, and CH4. These
impurities lower the phase transition temperature of CO2, which can even drop to under –80
°C. In this case, the refrigeration energy penalty increases substantially, and CO2 frost
formation becomes highly possible, thereby threatening equipment safety. Attention should
thus be paid to raising the phase transition temperature of CO2 to improve the cryogenic
separation method and consequently avoid facility freezing problems and high energy penalty.

In the present work, we propose an improved CO2 separation and purification system that can
separate the majority of the CO2 in liquid state from the mixed gases with relatively low energy
penalty via multi-stage compression, refrigeration, and separation. Furthermore, by introducing
high pressure and near ambient temperature distillation into the improved system, CO2 purity
in the final product reaches 99.9%.

3.2 PRE-COMBUSTION CAPTURE

Pre-combustion efforts are mainly focused on methods of advanced solvents, solid sorbents,
and membrane systems for the separation of H2 and CO2, with specific emphasis on high-
temperature/novel materials, process intensification, and nanomaterials. Additionally, novel
concepts, such as hybrid technologies that combine attributes from multiple technologies (e.g.,
sorbents and membranes) are being investigated.

Solvent-based CO2 capture involves chemical or physical absorption of CO2 from syngas into
a liquid carrier and regenerating the absorption liquid by increasing the temperature or reducing
the pressure to break the absorbent-CO2bond. R&D objectives include modifying regeneration
conditions to recover the CO2 at a higher pressure, improving selectivity to reduce H2 losses,
and developing a solvent that has a high CO2 loading at a higher temperature to improve IGCC
efficiency.

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Sorbent technologies under development are aimed at improving the cost and performance of
IGCC CO2 separation. R&D objectives are for sorbents to maintain a high adsorption loading
capacity, be resistant to attrition over multiple regeneration cycles, and exhibit good
performance at the high temperatures encountered in IGCC systems to avoid the need for
syngas cooling and reheating.

Membrane technology options are under development to separate CO2 and H2 in coal derived
syngas. Membrane designs include metallic, polymeric, or ceramic materials operating at
elevated temperatures and using a variety of chemical and/or physical mechanisms for
separation. R&D objectives are membranes that have high permeability and selectivity with
low pressure drop, tolerance to contaminants (e.g., sulphur), and are capable of operation at
system temperatures up to 500 °F.

Novel Concepts are under investigation and include hybrid systems that combine attributes
from multiple technologies, novel process conditions (e.g., systems that operate at sub ambient
temperatures), and nanomaterials. Technologies being considered include combining
temperature-swing and pressure-swing regeneration to lower cost and energy penalties and
integrating capture directly with the water-gas shift reaction to help drive equilibrium toward
CO2 and H2production while eliminating the need for syngas cooling.

4. TRI-REFORMING OF METHANE

The tri-reforming process is a three-step reaction process. It avoids the separation step and
has the promise of being cost-efficient for producing industrially useful synthesis gas.

4.1 WHY USING FLUE GAS?

Flue gases from fossil fuel-based electricity-generating units are the major concentrated CO2
sources. If CO2 is to be separated, as much as 100 megawatts of a typical 500-megawatt
coalfired power plant would be necessary for today’s CO2 capture processes based on the
alkanolamines. Therefore, it would be highly desirable if the flue gas mixtures can be used for

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CO2 conversion but without pre-separation of CO2. CO2 conversion and utilization should be
an integral part of CO2 management, although the amount of CO2 that can be used for making
industrial chemicals is small compared to the quantity of flue gas. There appears to be a unique
advantage of directly using flue gases, rather than using pre-separated and purified CO2 from
flue gases, for the proposed tri-reforming process. Typical flue gases from natural gas-fired
power plants may contain 8-10% CO2, 18-20% H2O, 2-3% O2, and 67-72% N2; typical flue
gases from coal-fired boilers may contain 12-14 vol% CO2, 8-10 vol% H2O, 3-5 vol % O2
and 72-77% N2. The typical furnace outlet temperature of flue gases is usually around 1200°C
which will decrease gradually along the pathway of heat transfer, while the temperature of the
flue gases going to stack is around 150°C. Pollution control technologies can remove the SOx,
NOx and particulate matter effectively, but CO2 and H2O as well as O2 remain largely
unchanged.

4.2 CONCEPT OF TRI-REFORMING

Tri-reforming is a synergetic combination of endothermic CO2 reforming (eq. 1) and steam


reforming (eq. 2) and exothermic partial oxidation of methane (eq. 3, eq. 4). CO2, H2O and
O2 in the waste flue gas from fossil-fuel-based power plants will be utilized as co-reactants for
tri-reforming of natural gas for the production of
synthesis gas.

Tri-reforming of Natural Gas:

CH4 + CO2 = 2 CO + 2 H2 [Endo: ΔH°= 247.3 kJ/mol] (1)


CH4 + H2O = CO + 3 H2 [Endo:ΔH° = 206.3 kJ/mol] (2)
CH4+ 1/2 O2 = CO + 2 H2 [Exo:ΔH° = - 35.6 kJ/mol] (3)
CH4 + 2 O2 = CO2 + 2 H2O [Exo:ΔH° = - 880 kJ/mol] (4)

Reactions for Coke Formation and Destruction:

CH4 = C + 2 H2 [Endo: ΔH° = 74.9 kJ/mol] (5)


2 CO = C + CO2 [Exo: ΔH° = - 172.2 kJ/mol] (6)
C + CO2 = 2 CO [Endo: ΔH° = 172.2 kJ/mol] (7)

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C + H2O = CO + H2 [Endo: ΔH° = 131.4 kJ/mol] (8)
C + O2 = CO2 [Exo: ΔH° = -393.7 kJ/mol] (9)

Fig. 1 illustrates the tri-reforming concept as a new approach to CO2 conversion using flue
gases for syngas production. The tri-reforming is a synergetic combination of three catalytic
reforming reaction processes. Coupling CO2 reforming and steam reforming can give syngas
with desired H2/CO ratios for methanol (MeOH) and Fischer-Tropsch (F-T) synthesis.
Synthesis gas (syngas) can be made using natural gas, coal, naphtha, and other carbon-based
feedstocks by various processes. Steam reforming of methane, partial oxidation of methane,
CO2 reforming of methane, and auto-thermal reforming of methane are the representative
reaction processes for syngas production from natural gas.

The combination of dry reforming with steam reforming can accomplish two important
missions: to produce syngas with desired H2/CO ratios and to mitigate the carbon formation
problem that is significant for dry reforming. Integrating steam reforming and partial oxidation
with CO2 reforming could dramatically reduce or eliminate carbon formation on reforming
catalyst thus increase catalyst life and process efficiency. Therefore, the proposed tri-reforming
can solve two important problems that are encountered in individual processing. The
incorporation of O2 in the reaction generates heat in situ that can be used to increase energy
efficiency and O2 also reduces or eliminates the carbon formation on the reforming catalyst.
The tri-reforming can thus be achieved with natural gas and flue gases using the ‘waste heat’
in the power plant and the heat generated in situ from oxidation with the O2 that is already
present in flue gas.

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Fig. 2. Process concept for tri-reforming of natural gas using flue gas from fossil fuel-based power plants.
HT represents heat transfer or heat exchange including reactor heat up and waste heat utilization

4.3 THERMODYNAMICS OF TRI-REFORMING REACTIONS

Table 1 shows the equilibrium conversions and the product H2/CO molar ratios calculated
using HSC program [10,11] for tri-reforming under atmospheric pressure. It is possible to
perform tri-reforming with over 95% CH4 conversion and over 80% CO2 conversion at 800-
850 °C when the ratio of CO2 and H2O is close to 1.0, O2/CH4= 0.1, and the ratio of
(CO2+H2O+O2)/CH4 = 1.05. This is close to the cases with compositions of flue gases.

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Table 1. Equilibrium CO2 and CH4 conversions and product H2/CO molar ratios for tri-reforming of
CH4 with CH4: CO2: H2O: O2 =1:0.475:0.475:0.1 at 850C under 1 atm.

Reaction Equilibrium

CH4 Conv. H2/CO Mol


Temperature °C CO2 conv. (%)
(%) Ratio

850 98.54 84.50 1.71

800 96.00 81.10 1.72

750 90.70 73.33 1.77

700 86.00 55.60 2.14

4.4 FEASIBILITY OF TRI-REFORMING OF CO2

Computational analysis shows there are benefits of incorporating steam (H2O) and oxygen
(O2) simultaneously in CO2 reforming of CH4. Prior works have established that CO2
reforming encounters carbon formation problem, even with noble metal catalysts, particularly
under elevated pressure. Recent laboratory studies with pure gases have shown that the addition
of oxygen to CO2 reforming or the addition of oxygen to steam reforming of CH4 can have
some beneficial effects in terms of improved energy efficiency or synergetic effects in
processing and in mitigation of coking. Researchers have studied energy-efficient H2
production by simultaneous catalytic combustion and catalytic CO2-H2O reforming of
methane using mixture of pure gases including CH4, CO2, H2O and O2. Recent studies have
shown that it is possible to convert methane into syngas with high conversion and high
selectivity for both CO and H2. There are also reports suggesting that a Pt/ZrO2 catalyst is
active for steam and CO2 reforming combined with partial oxidation of methane. Therefore,
tri-reforming seems feasible.

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5. CATALYSTS FOR TRI-REFORMING
REACTIONS

Figs. 2, 3 and 4 show the CH4 conversion, CO2 conversion, and H2/CO ratio in the
products, respectively, for tri-reforming over Ni/MgO, Ni/ZrO2, Ni/CeO2, Ni/CeZrO and
Ni/MgO/CeZrO catalysts as well as Ni/Al2O3 catalyst. The feed for tri-reforming had the
composition of CH4: CO2: H2O: O2 (mole ratio) = 1:0.48:0.54:0.1. Almost equal amounts of
CO2 and H2O in the feed were selected for the convenience of comparing CO2 conversions in
the presence of an equal amount of H2O in tri-reforming. The tri-reforming reactions were
conducted at 700ºC – 850ºC and 1 atm. Under all these reaction conditions, CH4 and CO2
conversions are very dependent on the type of catalysts used, but O2 conversion is always
100%. Ni/MgO and Ni/MgO/CeZrO show the highest CO2 conversion in general (Fig. 3).

Ni/MgO/CeZrO, Ni/ZrO2, and Ni/Al2O3 (ICI catalyst) give almost the same CH4 conversions
at 800ºC – 850ºC, while Ni/CeO2 and Ni/CeZrO have relatively lower CH4 conversions
(Fig.2). With the reaction temperature decreasing, CH4 conversion over Ni/MgO declines
much faster than that over other catalysts. At 700ºC, the CH4 conversion over Ni/MgO is the
lowest among all the tested catalysts. The deactivation of Ni/MgO at lower temperatures cause
the fast decline of CH4 conversion over Ni/MgO and the deactivation is caused by the re-
oxidation of Ni. This is justified by the facts that NiO in the NiO/MgO catalyst is not reducible
at temperature below 50ºC and no carbon formation is observed on the used Ni/MgO catalyst.
In addition, metal sintering may not be the reason for deactivation because all the catalytic
performance tests were first carried out at 850ºC.

Among all the catalysts tested, Ni/CeO2 has the second lowest CH4 conversion at reaction
temperatures above 750ºC. The low CH4 conversion over Ni/CeO2 is probably related to the
larger Ni particles over Ni-CeO2 or the occurring of strong metal-support interaction (SMSI)
due to the partial reduction of CeO2 at high temperatures. Surprisingly, Ni/CeZrO has the
lowest CH4 conversion. Although Ni/MgO, Ni/MgO/CeZrO, Ni/Al2O3, and Ni/ZrO2 have
similar CH4 conversions, their CO2 conversions are quite different. Ni/MgO shows the highest
CO2 conversion at temperatures above 750ºC, followed by Ni/MgO/CeZrO. Ni/CeO2 and
Ni/CeZrO again show the lowest CO2 conversion.

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The H2/CO ratio in the products depends mainly on the CO2 and H2O conversions in tri-
reforming. If more H2O is converted than CO2, then the H2/CO ratio in the product would be
higher. Similarly, if less H2O is converted than CO2, the H2/CO ratio would be lower.
Therefore, the H2/CO ratio is a good indicator for comparing the ability to convert CO2 in the
presence of H2O over different catalysts. Ni/MgO gives the lowest H2/CO ratio, followed by
Ni/MgO/CeZrO (shown in Fig. 4). The H2/CO ratios over Ni/CeO2, Ni/ZrO2, and Ni/Al2O3
(ICI catalyst) are similar and slightly higher than Ni/MgO/CeZrO. Ni/CeZrO gives the highest
H2/CO ratio. These results strongly suggest that Ni/MgO enhance the CO2 conversion most in
the presence of H2O and O2.
Among the tested catalysts, their ability to enhance the conversion of CO2 follows the order of

Ni/MgO > Ni/MgO/CeZrO > Ni/CeO2 ≈ Ni/ZrO2 ≈ Ni/Al2O3 (ICI) > Ni/CeZrO.

The different ability to convert CO2 over different catalysts in tri-reforming is related to the
properties of the catalysts. The enhancement of CO2 conversion over Ni/MgO might be related
to its enhanced CO2 adsorption ability. However, catalysts supported on CeZrO (e.g.,
Ni/MgO/CeZrO and Ni/CeZrO) do not show more enhancement of CO2 conversion than
Ni/MgO even though these catalysts demonstrate more and stronger CO2 adsorption than
Ni/MgO as indicated by the large CO2 desorption peaks at 710-717ºC.

Fig. 3. CH4 conversions in the tri-reforming reaction over 100 mg supported Ni catalysts at 1 atm and
feed composition of CH4 : CO2 : H2O : O2 = 1 : 0.48 : 0.54 : 0.1 (CH4 flow rate = 25 ml/min)

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Fig. 4. CO2 conversions in the tri-reforming reaction over 100 mg supported Ni catalysts at 1 atm and
feed composition of CH4 : CO2 : H2O : O2 = 1 : 0.48 : 0.54 : 0.1 (CH4 flow rate = 25 ml/min)

Fig. 5. H2/CO ratios in the tri-reforming reaction over 100 mg supported Ni catalysts at 1 atm and
feed composition of CH4: CO2: H2O: O2 = 1 : 0.48 : 0.54 : 0.1 (CH4 flow rate = 25 ml/min)

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6. ENERGY CONSUMPTION OF TRI-REFORMING
PROCESS

A comparative energy analysis by calculation indicated that tri-reforming is more desired for
producing syngas with H2/CO ratios of 1.5-2.0 compared to CO2 reforming and steam
reforming of methane, in terms of less amount of energy required and less net amount of CO2
emitted in the whole process for producing synthesis gas with H2/CO ratio of 2.0 [ 8]. The tri-
reforming process could be applied, in principle, to the natural gas-based power plants and
coal-based power plants.

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7. CONCLUSION

Catalytic tri-reforming of methane can be achieved successfully with high CH4 conversion
(>97%) and high CO2 conversion (>80%) for producing syngas with desired H2/CO ratios of
1.5-2.0 over supported nickel catalysts at 800-850 °C under atmospheric pressure without the
problem of carbon formation on the catalyst. The CO2 and CH4 conversion as well as H2/CO
ratios of the products from tri-reforming also depend on the type and nature of catalysts.

An important observation is that CO2 conversion can be maximized by tailoring catalyst


composition and preparation method. In other words, certain catalysts with proper feature can
give much higher CO2 conversion than other catalysts under the same reaction conditions
with the same reactants feed. Among all the catalysts tested for tri-reforming, their ability to
enhance the conversion of CO2 follows the order of

Ni/MgO > Ni/MgO/CeZrO > Ni/CeO2 ≈ Ni/ZrO2 ≈ Ni/Al2O3 (ICI) > Ni/CeZrO

The different ability to convert CO2 over different catalysts in tri-reforming is related to the
properties of the catalysts. Results of catalytic performance tests over Ni/MgO/CeZrO
catalysts at 850ºC and 1 atm at different feed compositions confirm the predictions based on
the thermodynamic analysis for equilibrium conversions in tri-reforming of methane. Further
studies on improving catalysts are necessary for understanding the factors affecting CO2
conversion and CH4 in the presence of steam and oxygen during tri-reforming.

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